Mathematical models suggest that the strain along the film formed by parallel passes of a nanoindentation probe in contact with the film can be either homogenous or heterogeneous, depending on contact pressure and spacing between passes. Here, in this study, a 1 µm copper thin film was worn with a cono-spherical diamond probe with normal loads ranging from 25 to 800 µN and wear box edge lengths of 40, 60, and 80 µm. The nanoindenter counterface was rastered across the surface to mimic dry sliding wear. To determine potential strain field changes, 10-step quasi-static indents (200–2000 µN) were performed using nanoindentation inside the wear boxes created at various loads to determine if a strain field alteration could be observed in changes in hardness of the copper thin film. It was shown that there was a softening effect in the hardness for normal loads < 400 µN used during nanowear compared to the as-deposited copper. Normal loads ≥ 400 µN had a similar or higher hardness than the as-deposited copper. This is believed to have occurred due to a relaxation in the residual stresses created during deposition in the copper thin films at lower loads, which caused a decrease in hardness.more » Conversely, at the higher loads, increased deformation leads to an increase in hardness. Lastly, all of the wear boxes displayed a higher estimated strain hardening exponent than the as-deposited material.« less

@article{osti_1422927,
title = {Tribological performance of monolithic copper thin films during nanowear},
author = {Schultz, Bradley M. and Li, Nan and Economy, David R. and Sharp, Julia L. and Mara, Nathan A. and Kennedy, Marian S.},
abstractNote = {Mathematical models suggest that the strain along the film formed by parallel passes of a nanoindentation probe in contact with the film can be either homogenous or heterogeneous, depending on contact pressure and spacing between passes. Here, in this study, a 1 µm copper thin film was worn with a cono-spherical diamond probe with normal loads ranging from 25 to 800 µN and wear box edge lengths of 40, 60, and 80 µm. The nanoindenter counterface was rastered across the surface to mimic dry sliding wear. To determine potential strain field changes, 10-step quasi-static indents (200–2000 µN) were performed using nanoindentation inside the wear boxes created at various loads to determine if a strain field alteration could be observed in changes in hardness of the copper thin film. It was shown that there was a softening effect in the hardness for normal loads < 400 µN used during nanowear compared to the as-deposited copper. Normal loads ≥ 400 µN had a similar or higher hardness than the as-deposited copper. This is believed to have occurred due to a relaxation in the residual stresses created during deposition in the copper thin films at lower loads, which caused a decrease in hardness. Conversely, at the higher loads, increased deformation leads to an increase in hardness. Lastly, all of the wear boxes displayed a higher estimated strain hardening exponent than the as-deposited material.},
doi = {10.1016/j.wear.2017.10.005},
journal = {Wear},
number = C,
volume = 394-395,
place = {United States},
year = {2017},
month = {10}
}

N-doped ZnO thin films were deposited on 304L stainless steel through the pyrolysis of zinc acetate and ammonium acetate in different ratios at a temperature of 420 degrees C using metal organic chemical vapor deposition. Compositional and structural analyzes of the films were performed by using Rutherford backscattering spectroscopy and X-ray diffraction. The frictional behavior of the thin films and 304L stainless steel substrate was evaluated using a ball-on-flat configuration with reciprocating sliding under marginally lubricated and fully flooded conditions. Al alloy (2017) was used as ball counterface, while basestock synthetic polyalfaolefin oil (PAO10) without additives was used as lubricant.more » The flat and ball counterface surfaces were examined to assess the wear dimension and failure mechanism. Under marginally lubricated condition, N-doped ZnO thin films provided significant reduction in friction, whereas the films have minimal or no effect in friction under fully flooded condition. N-doped ZnO thin films showed a significant effect in protecting the ball counterface as wear volume was reduced compared with that of the substrate under the marginally lubricated condition. Under the fully flooded condition, with the exception of one of the films, the wear volume of the N-doped ZnO thin films ball reduced compared with that of the substrate. In all the ball counterfaces for N-doped ZnO thin films under both conditions, wear occurred through abrasive mechanism of various degrees or mild polishing. Thus, superfluous lubrication of N-doped ZnO thin films is not necessary to reduce friction and wear.« less

Mechanical properties of thin films are often obtained solely from nanoindentation. At the same time, such measurements are characterized by a substantial amount of uncertainty, especially when mean pressure or hardness are used to infer uniaxial yield stress. In this paper we demonstrate that indentation with a pyramidal flat tip (frustum) indenter near the free edge of a sample can provide a significantly better estimate of the uniaxial yield strength compared to frequently used Berkovich indenter. This is first demonstrated using a numerical model for a material with an isotropic pressure sensitive yield criterion. Numerical simulations confirm that the indentermore » geometry provides a clear distinction of the mean pressure at which a material transitions to inelastic behavior. The mean critical pressure is highly dependent on the plastic Poisson ratio ν p so that at the 1% offset of normalized indent depth, the critical pressure p mc normalized to the uniaxial yield strength σ 0 is 1 < p mc/σ 0 < 1.3 for materials with 0 < ν p < 0.5. Choice of a frustum over Berkovich indenter reduces uncertainty in hardness by a factor of 3. These results are used to interpret frustum indentation experiments on nanoporous (NP) Copper with struts of typical diameter of 45 nm. An estimate of the yield strength of NP Copper is obtained 230 MPa < σ 0 < 300 MPa. Edge indentation further allows one to obtain in-plane strain maps near the critical pressure. Finally, comparison of the experimentally obtained in-plane strain maps of NP Cu during deformation and the strain field for different plastic Poisson ratios suggest that this material has a plastic Poisson ratio of the order of 0.2–0.3. However, existing constitutive models may not adequately capture post-yield behavior of NP metals.« less

Increasing the activity of Ag-based catalysts for the oxygen reduction reaction (ORR) is important for improving the performance and economic outlook of alkaline-based fuel cell and metal-air battery technologies. In this work, we prepare CuAg thin films with controllable compositions using e-beam physical vapour deposition. X-ray diffraction analysis indicates that this fabrication route yields metastable miscibility between these two thermodynamically immiscible metals, with the thin films consisting of a Ag-rich and a Cu-rich phase. Electrochemical testing in 0.1 M potassium hydroxide showed significant ORR activity improvements for the CuAg films. On a geometric basis, the most active thin film (Cumore »70Ag 30) demonstrated a 4-fold activity improvement versus pure Ag at 0.8 V vs the reversible hydrogen electrode. Furthermore, enhanced ORR kinetics for Cu-rich (> 50at % Cu) thin films was demonstrated by a decrease in Tafel slope from 90 mV/dec, a commonly observed value for Ag catalysts, to 45 mV/dec. Surface enrichment of the Ag-rich phase after ORR testing was indicated by x-ray photoelectron spectroscopy and grazing incidence synchrotron x-ray diffraction measurements. Here, by correlating density functional theory with experimental measurements, we postulate that the activity enhancement of the Cu-rich CuAg thin films arises due to the non-equilibrium miscibility of Cu atoms in the Ag-rich phase, which favourably tunes the surface electronic structure and binding energies of reaction species.« less

Microstructural evolution during the devitrification of amorphous tantalum thin films synthesized via pulsed laser deposition was investigated using in situ transmission electron microscopy (TEM) combined with ex situ isothermal annealing, bright-field imaging, and electron-diffraction analysis. The phases formed during crystallization and their stability were characterized as a function of the chamber pressure during deposition, devitrification temperature, and annealing time. A range of metastable nanocrystalline tantalum oxides were identified following devitrification including multiple orthorhombic oxide phases, which often were present with, or evolved to, the tetragonal TaO 2 phase. While the appearance of these phases indicated the films were evolving tomore » the stable form of tantalum oxide—monoclinic tantalum pentoxide—it was likely not achieved for the conditions considered due to an insufficient amount of oxygen present in the films following deposition. Nevertheless, the collective in situ and ex situ TEM analysis applied to thin film samples enabled the isolation of a number of metastable tantalum oxides. As a result, new insights were gained into the transformation sequence and stability of these nanocrystalline phases, which presents opportunities for the development of advanced tantalum oxide-based dielectric materials for novel memristor designs.« less

In order to tailor the assembling of polymers and organic molecules, a deeper understanding of the kinetics involved in thin film production is necessary. While post-production characterization only provides insight on the final film structure, more sophisticated experimental setups are needed to probe the structure formation processes in situ during deposition. The drying kinetics of a deposited organic thin film strongly influences the assembling process on the nanometer scale. Lastly, this work presents an experimental setup that enables fine control of the atmosphere composition surrounding the sample during slot die coating, while simultaneously probing the film formation kinetics using inmore » situ grazing incidence X-ray scattering and spectroscopy.« less